JP2002114920A - Aqueous polymer dispersion and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder for an adhesive, which produces a water-resistant and heat-resistant adhesive bond. SOLUTION: The aqueous polymer dispersion contains 0.0001-1 mol of hydrolyzable silicon group and 0.0001-1 mol of urea or thiourea group based on 100 g of a polymer in the dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous polymer dispersion, wherein each of the dispersions has a hydrolyzable silicon group of 0.0 with respect to 100 g of the polymer present in the dispersion.
001 to 1 mol and urea group or thiourea group 0.00
It is characterized by containing 0.1 to 1 mol.

The invention further relates to the use of the polymer dispersions as adhesives and sealing materials, in particular as binders for tile adhesives.

[0003]

EP 35 332 discloses binders for ceramic tiles containing hydrolyzable silicon groups resulting from the copolymerization of ethylenically unsaturated silicon compounds. European Patent Application Publication No. 366969
The specification describes binders which also have hydrolyzable silicon groups.

[0004] The inclusion of a hydrolyzable silicon compound enhances the water resistance of the adhesive bond.

It is desirable for the adhesive bond not only to have high water resistance, but also to have as high a heat resistance as possible. State-of-the-art binders are still insufficient with respect to heat resistance.

[0006] Polymers having urea groups are described, for example, in EP-A-184091.

[0007]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a binder for an adhesive which produces a water- and heat-resistant adhesive bond.

[0008]

The object is achieved by a polymer dispersion as described at the outset and a method of using the dispersion as a binder for adhesives and sealing materials, in particular for ceramic tiles.

The aqueous polymer dispersions according to the invention have at least 0.0001 mol, preferably at least 0.0005 mol, of urea or thiourea groups per 100 g of polymer dispersed in the dispersion, and Not more, preferably not more than 0.5 mol, more preferably 0.5 mol.
Not more than 1 mol, very advantageously not more than 0.05 mol, most preferably not more than 0.01 mol.

In particular, the groups considered are those of the formula I:

[0011]

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Wherein R ¹ and R ² independently represent a hydrogen atom or a C ₁ -C ₅ -alkyl group, or R ¹ and R ² together represent a bridged C ₂ -C ₄ -alkylene group Wherein the alkylene group is mono- or di-substituted by a C ₁ -C ₄ -alkoxy group or a hydroxyl group, and X is an oxygen atom or a sulfur atom).

Advantageously, R ¹ and R ² independently of one another represent a hydrogen atom or a C ₁ -C ₅ -alkyl radical, or R ¹ and R ² together represent a bridged C ₂ -C ₄ -alkylene radical. Represent. X preferably represents 0.

In a particularly preferred embodiment, R ¹ and R ² are together a C ₂ -C _4- linked to _two nitrogen atoms.
Represents an alkylene group, especially an ethylene group.

The urea group or thiourea group may be a component of a low molecular weight non-polymeric compound dissolved or dispersed in water as a dispersion medium.

In particular, these compounds have at least 2 and preferably 2 to 4 urea or thiourea groups.

Preferably, the urea or thiourea groups are attached to the polymer dispersed in the dispersion.

These polymers may be polycondensates, such as polyesters or addition polymers, such as polyurethanes.

Advantageously, these polymers are polymers obtained by radical or ionic polymerization of ethylenically unsaturated compounds (monomers) (ie radically polymerized polymers).

The urea or thiourea group may be attached to the polymer by, for example, a polymer-analogous reaction.

The preparation of the polymer is preferably carried out in the presence of suitable starting compounds which already have urea or thiourea groups. In a preferred embodiment comprising a radically polymerized polymer, the polymerization is advantageously carried out using monomers having urea or thiourea groups (monomer A).

These monomers have at least one, preferably one, copolymerizable ethylenically unsaturated group in addition to the urea or thiourea group.

This copolymerizable ethylenically unsaturated group in monomer A is advantageously a (meth) acryl group.

Suitable monomers A preferably have one copolymerizable ethylenically unsaturated group and one group of the formula I.

The compounds used advantageously are of the formula II:

[0026]

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(Wherein, R ³ represents a hydrogen atom or a methyl group, Y represents —O— or —NH—, R ⁴ is a divalent C ₁ -C ₁₀ -alkylene group, and R ¹ , R ² is as defined above).

Advantageously, R³Represents a hydrogen atom or a methyl group
Y represents -O-, R represents⁴Is C ₂~ C₆-Alkyre
A group represented by¹And R²Is C together₂~ C₄-Al
Represents a kylene group.

Ureidoethylene methacrylate (R ¹ ,
1- (2-methacryloxyethyl) imidazolin-2-one known as R ² = ethylene, Y = O, R ³ = methyl, R ⁴ = ethylene, abbreviation = UMA):

[0030]

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Alternatively, ureidoethylene acrylate is particularly preferred.

The aqueous polymer dispersions of the present invention further have hydrolyzable silicon groups, ie, silicon groups having at least one hydroxyl group directly bonded to the Si atom after hydrolysis.

In particular, formula III:

[0034]

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(Wherein, R ^{5 to} R ⁷ independently represent C ₁ to
C ₈ -alkyl or alkoxy groups, in particular C ₁ -C ₄
An alkyl group or an alkoxy group, provided that the group R ⁵
At least one of R ⁷ to R ⁷ is an alkoxy group).

In a particularly preferred embodiment, R ^{5 to} R
All ⁷ groups represent a C ₁ -C ₈ -alkoxy group, preferably a C ₁ -C ₄ -alkoxy group, in particular a methoxy group.

The content of hydrolyzable silicon groups in the aqueous polymer dispersion is from 0.0001 to 1 mol. Advantageously, this content is in each case 100 g of polymer dispersed in the dispersion
At least 0.0005 mol, based on the content, not more than 1 mol, preferably not more than 0.5 mol, more preferably not more than 0.1 mol, very preferably 0.05 mol Not more than mole, most preferably 0.0
Not more than 1 mole.

The molar ratio of urea or thiourea groups to silicon groups is preferably from 1:10 to 10: 1, more preferably from 1: 5 to 5: 1.

The hydrolyzable silicon group may be a component of the low molecular weight non-polymeric compound dissolved or dispersed in the water of the dispersant.

In particular, at least two of these compounds
It preferably has 2 to 4 hydrolysable silicon groups. However, if these compounds have only one hydrolysable silicon group, this silicon group preferably has at least two hydrolysable groups.

The hydrolyzable silicon groups are preferably attached to the polymer. Very preferably urea or thiourea groups and hydrolyzable silicon groups are attached to the polymer.

In an advantageous embodiment comprising a radically polymerized polymer, monomers having hydrolyzable silicon groups can be used, for example, as comonomer (monomer B) in the polymer dispersion. For example, one -S-
Polymerization regulators having an H group and one hydrolyzable silicon group (Modifier B) are suitable.

These polymerization regulators B are bonded to the ends of the polymer chains during radical polymerization.

Suitable monomers B are for example of the formula IV:

[0045]

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Wherein Z is a vinyl group (H ₂ C ＝ CH—), an acryl group:

[0047]

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Or a methacrylic group:

[0049]

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Wherein Y represents a bonding group having up to 20 carbon atoms, but when Z represents a vinyl group, Y may be omitted and R ^{5 to} R ⁷ represent those described above. .

Advantageously, Z represents a (meth) acryl group,
Y is _C 1 -C ₆ - represents an alkylene group.

Suitable regulators B are, for example, those of the formula V:

[0053]

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A regulator of the formula:⁸And R⁹Is
A hydrogen atom or C independently of each other₁~ C ₄-Alkyl group
Wherein n is a number from 0 to 10, advantageously from 1 to 8,⁵
~ R⁷Represents the above.

The polymer dispersed in the polymer dispersion according to the invention is advantageously a radically polymerized polymer.

The radically polymerized polymer preferably contains at least 40% by weight, preferably at least 60% by weight and very preferably at least 80% by weight, of so-called main monomers.

The main monomers are C ₁ -C ₂₀ -alkyl (meth) acrylates, vinyl esters of carboxylic acids having up to 20 carbon atoms, vinyl aromatic compounds having up to 20 carbon atoms, ethylenically unsaturated Nitriles, vinyl halides, vinyl ethers of alcohols having 10 to 10 carbon atoms, having 2 to 8 carbon atoms,
And selected from the group consisting of aliphatic hydrocarbons having one or two double bonds or mixtures of these monomers.

The following compounds are described by way of example. C ₁
-C ₁₀ - alkyl (meth) acrylate having an alkyl group, for example methyl methacrylate, methyl acrylate, n- butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

In particular, mixtures of alkyl (meth) acrylates are suitable.

Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl esters of versatic acid and vinyl acetate.

Suitable vinyl aromatic compounds are vinyl toluene, α-methylstyrene and p-methylstyrene,
α-butylstyrene, 4-n-butylstyrene, 4-n
-Decylstyrene, preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.

Vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.

The vinyl ethers that can be described are:
For example, vinyl methyl ether or vinyl isobutyl ether. Preference is given to vinyl ethers of alcohols having 1 to 4 carbon atoms.

As hydrocarbons having 2 to 8 carbon atoms and 2 olefinic double bonds, butadiene, isoprene and chloroprene can be described, and hydrocarbons having one double bond are, for example, ethylene And propylene.

The main monomers are advantageously C ₁ -C _10-
Alkyl (meth) acrylates, especially C ₁ -C ₈ -alkyl (meth) acrylates and vinyl aromatic compounds,
In particular, styrene and mixtures thereof.

Methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n
-Hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, styrene and mixtures of these monomers are very advantageous.

In addition to the main monomer, the radically polymerized polymer can have other monomers, for example, monomers having carboxylic, sulfonic or phosphonic groups. Preference is given to monomers having a carboxylic acid group. As examples, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid can be mentioned.

Other monomers are, for example, monomers having hydroxyl groups, in particular C ₁ -C ₁₀ -hydroxyalkyl (meth) acrylates and (meth) acrylamides.

Further examples of other monomers include phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate and amino (meth) acrylates, such as 2-aminoethyl (meth) acrylate.

[0070] Other possible monomers include crosslinking monomers.

In the preferred embodiment described above, monomers having urea or thiourea groups or monomers having hydrolyzable silicon groups are used.

The production of the radically polymerized polymer is in a preferred embodiment carried out by emulsion polymerization, so that the polymer is an emulsion polymer.

However, the production can be carried out selectively, for example, by solution polymerization followed by dispersion in water.

In emulsion polymerization, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surfactant compounds.

A detailed description of suitable protective colloids can be found in Ho
uben-Weyl, Method der or
ganischen Chemie XIV / 1, Ma
cromolecular Materials Ge
org-Thieme-Verlag Stuttga
rt, 1961, 411-420. Suitable
Suitable emulsifiers are anionic, cationic and nonionic
Is an emulsifier. Advantageously, as a supplemental surfactant,
The molecular weight is different from the protective colloid.
/ Mol is used. Of course surface activity
When using a mixture of agents, the individual components are compatible with each other.
Must be tested, which may require some preliminary testing
Can be inspected. Advantageously as a surfactant
Anionic and nonionic emulsifiers are used. General
Supplementary emulsifiers used for, for example, ethoxylated fats
Alcohol (C₈~ C₃₆Ethoxy, consisting of alkyl
Degree of silation: 3 to 50), ethoxylated mono-, di-
And tri- (C₄~ C₉-Alkyl) phenol (d)
Degree of toxylation: 3-50), dia of sulfosuccinic acid
Alkali metal salts of alkyl esters and (C₈~ C₁₂
-Alkyl) sulfate alkali metal salts and anions
Monium salt, ethoxylated C₁₂~ C₁₈-Arcano
(The degree of ethoxylation: 4 to 30) alkali metal salt
And ammonium salts, ethoxylated (C₄~ C₉-A
Alkyl) phenol (degree of ethoxylation: 3 to 50)
Alkali metal and ammonium salts of₁₂~ C
₁₈-Alkyl) sulfonic acid alkali metal salts and a
Ammonium salt and (C₉~ C ₁₈-Alkyl) ally
Alkali metal and ammonium salts of sulfonic acid
is there.

Other suitable emulsifiers have the general formula II:

[0077]

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Wherein R ⁵ and R ⁶ represent a hydrogen atom or C ₄ -C ₁₄ -alkyl, but neither represents a hydrogen atom, and X and Y are an alkali metal ion and / or Alternatively, it may be an ammonium ion. Advantageously, R ⁵ and R ⁶ represent a linear or branched alkyl group having ⁶ to 18 carbon atoms, in particular 6, 12, and 16 carbon atoms or a hydrogen atom,
R ⁵ and R ⁶ do not both represent a hydrogen atom.
X and Y are preferably sodium, potassium or ammonium ions, with sodium ions being particularly preferred. X and Y represent sodium;
⁵ is a branched alkyl group having 12 carbon atoms, and R ⁶ is a hydrogen atom or R ⁵
I is particularly preferred. Monoalkylated products 50-90
Technical mixtures having a weight percentage of, for example, Dowfa
x (R) 2A1 (a registered trademark of Dow Chemical Company) is often used.

Suitable emulsifiers are Houben-Wey
l, Method der organische
n Chemie XIV / 1, Macromolec
ullar Materials Georg-Thie
me-Verlag Stuttgart, 1961,
192-208.

The trade name of the emulsifier is, for example, Dowfax
(R) 2A1, Emulan (R) NP50, Dext
rol (R) OC50, Emulsifier 825,
Emulsifier 825S, Emulan (R) O
G, Texapol (R) NSO, Nekanil
(R) 904S, Lumiten (R) I-RA, Lu
mitenE3065, Disponil FES77,
LutensolAT18, Steinapol VSL
And Emulphor NPS25.

The surfactants are generally used in amounts of 0.1 to 10% by weight, based on the monomers to be polymerized.

Water-soluble initiators for the emulsion polymerization are, for example, ammonium and alkali metal salts of peroxydisulfate, such as sodium peroxydisulfate, hydrogen peroxide or organic peroxides, such as t-butyl hydroperoxide.

So-called redox (reduction-oxidation) initiator systems are also suitable.

The redox initiator system is composed of at least one generally inorganic reducing agent and at least one inorganic or organic oxidizing agent.

The oxidizing component is, for example, the initiator of the emulsion polymerization already described.

The reducing component is, for example, an alkali metal salt of sulfurous acid, for example, sodium sulfite, sodium bisulfite,
Alkali metal disulfites, for example sodium disulfite, disulfite adducts of aliphatic aldehydes and ketones, for example acetone disulfite, or reducing agents, for example hydroxymethanesulfinic acid and its salts or ascorbic acid. Redox initiator systems can be used with soluble metal compounds in which the metal component exists in more than one valence state.

Common redox initiator systems are, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, t-butyl hydroperoxide / sodium disulfite, t-butyl hydroperoxide / sodium hydroxymethanesulfinate. . The individual components, for example the reducing component, may be a mixture, for example a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.

The compounds are often used in the form of an aqueous solution, the lower concentration limit being determined by the amount of water allowed in the dispersion and the higher concentration limit being determined by the solubility of the respective compound in water. It is determined. In general, the concentration is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the solution.
%, More preferably 1.0 to 10% by weight.

The amount of initiator is generally from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, based on the monomers to be polymerized.
It is. Alternatively, many different initiators can be used for the emulsion polymerization.

During the polymerization, the regulator can be used, for example, in an amount of 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized, whereby the molecular weight is reduced. Suitable compounds are, for example, compounds having a thiol group, for example t-butylmercaptan, ethyl thioglycolate, mercaptoethinol, mercaptopropyltrimethoxysilane or t-dodecylmercaptan.

The emulsion polymerization is generally carried out at from 30 to 130 ° C. and preferably from 50 to 90 ° C. The polymerization medium may consist of water alone or of a mixture of water and a water-miscible liquid such as methanol. Advantageously, only water is used. Emulsion polymerization can be carried out in the form of a batch process or a flow-through process including stepwise or gradient processing. A portion of the polymerization composition is placed in a reactor and heated to the polymerization temperature to initiate polymerization, after which the remainder of the polymerization composition generally comprises one or more feed streams containing monomers in pure or emulsified form. Preference is given to an inflow process in which the polymerization zone is fed continuously, stepwise or in a superimposed concentration gradient via a plurality of spatially separated feed streams, while maintaining the polymerization. The particle size achieved during the polymerization can be fine-tuned by the use of the polymer species in the first batch.

Methods of supplying an initiator to the polymerization vessel during the course of the free-radical aqueous emulsion polymerization are well known to those skilled in the art. It can be placed in the polymerization vessel as a whole batch or fed continuously or stepwise, depending on the degree consumed during the free-radical aqueous emulsion polymerization. Specifically, this depends on the chemistry of the initiator system and the polymerization temperature. Advantageously, a portion is used in the first batch and the remainder is fed to the polymerization zone to the extent consumed.

In order to remove residual monomers, an initiator is generally added after the end of the emulsion polymerization, ie after at least 95% conversion of the monomers has been achieved.

The individual components can be fed to the reactor during the inflow step, from above, from the side, or from below via the bottom of the reactor.

During the emulsion polymerization, the solids content is generally from 15 to 7
This gives an aqueous dispersion of the polymer having 5% by weight, preferably 40-75% by weight.

To obtain a high space-time yield of the reactor, dispersions having the highest possible solids content are advantageous. 6
In order to achieve a solids content higher than 0% by weight, the particle size should be bimodal or multimodal, otherwise the viscosity is too high and the dispersion can no longer be processed easily.
The production of new particle generations, for example, by the addition of seeds (EP
No. 81083), by adding an excess amount of an emulsifier or by adding a miniemulsion.
Another advantage achieved by low viscosity and high solids content is improved coating properties at high solids content. 1
The production of the new generation of particles or more can take place at any time. This is determined by the particle size distribution required to produce a low viscosity.

The radically polymerized polymers thus prepared are preferably used in the form of their aqueous dispersions.

The preparation of the polymer dispersions according to the invention can be carried out, for example, by mixing a) various polymers, for example various polymer dispersions as obtained by emulsion polymerization (especially when one of the polymers has urea groups or B) a low molecular weight compound having a urea group or a thiourea group, which has a thiourea group, and the other polymer may have a hydrolyzable silicon group.
Addition to an aqueous polymer dispersion, for example as obtained by emulsion polymerization, in which case the dispersed polymer can already have hydrolyzable silicon groups, c) similar to b), except that low molecular weight compounds The polymer having a hydrolyzable silicon group and the polymer having a urea group or a thiourea group; d) a low molecular compound having a urea group or a thiourea group and a low molecular compound having a hydrolyzable silicon group By addition to the polymer dispersion, e) in an advantageous embodiment both urea or thiourea groups and hydrolyzable silicon groups are attached to the polymer, in which case the polymer dispersion according to the invention is, for example, It can be produced in a simple manner by directly producing it as a product of emulsion polymerization by using an appropriate monomer (see above).

The polymer dispersions according to the invention are suitable for use as binders for various applications, for example as binders for paints, for example paint or paper coating materials.

It is particularly suitable for use as a binder for adhesives and sealing materials, especially for ceramic tile adhesives.

When used as a sealing material, the polymer in the aqueous dispersion is preferably from -60 ° C to + 40 ° C, more preferably from -60 ° C to + 10 ° C, particularly preferably from -55 ° C to + 55 ° C.
It has a glass transition temperature of -5C.

The glass transition temperature can be determined by common methods such as differential thermal analysis or differential scanning calorimetry (see, eg, ASTM 3418/82, midpoint temperature).

When used as an adhesive for ceramic tiles, the glass transition temperature is advantageously between -10 ° C. and +20.
° C.

When used as a binder for sealing materials or adhesives, inorganic fillers are advantageously added to the polymer dispersions according to the invention.

As fillers, aluminum silicate, quartz,
Mention may be made of precipitated or pyrogenic silicic acid, light and heavy spar, talc, dolomite, advantageously calcium carbonate. For example, encapsulants include coloring fillers such as titanium white, graphite, zinc white, lithopone and antimony white, iron oxide black, manganese black, cobalt black, antimony black and carbon black, chrome yellow, lead, zinc yellow. , Zinc green, pink pigments, cadmium red, cobalt blue, plush blue, ultramarine blue, manganese violet, cadmium yellow, molybdenum orange and strontium yellow.

When a dispersion is used as an adhesive for ceramic tiles, the weight of the filler is preferably 100 to 3000 parts by weight, more preferably 200 to 2000 parts by weight, per 100 parts by weight of the polymer. is there.

When a dispersion is used as a sealing material,
The weight of filler is preferably from 50 to 2000 parts by weight, based on 100 parts by weight of polymer.

Other auxiliaries which can be added to the polymer dispersion for the respective use are, for example, plasticizers, leveling agents, thickeners and the like.

The use of the polymer dispersions according to the invention is water-resistant and results in heat-resistant coatings, seals and adhesive bonds.

[0110]

EXAMPLES I. Preparation of Polymer Dispersion Base Composition (V1) First batch: polystyrene seeds 10.6 g water 280 g feed stream 2 2.8 g feed stream 1: water 265 g Dowfax® 2A1 (45%), Emulsifier (see above) 38.9 g Disponil® FES77 (30%), ethoxylated fatty alcohol (emulsifier) 5.8 g acrylic acid 7 g 3-methacryloxypropyltrimethoxysilane (MEMO) 3.5 g styrene 344.75 g ethylhexyl 344.75 g acrylate Feed stream 2: 26.6 g water 1.4 g sodium peroxosulfate.

The first batch was polymerized initially for 5 minutes, after which feeds 1 and 2 were started simultaneously and 180
Feed over minutes. The polymerization is then continued at 85 ° C. for a further 3
Continued for 0 minutes, after which the mixture was chemically deodorized and neutralized.

The production of test materials D1 to D3 and V2 was carried out in a similar manner.

In the test materials D1 to D3 of the present invention,
Ureidoethylene methacrylate (UMA) (25% in methyl methacrylate) was added to feed 1 in the amounts shown in Table 1.

Therefore, the amount of styrene in the basic composition was reduced.

In Comparative Test Material V2, no MEMO was used, and only 28 g of UMA was used.

Table 1: MEMO and UMA in polymers
Amount of

[0117]

[Table 1]

The other test material D4 was carried out in the same manner.

First batch: polystyrene seeds 10.6 g water 280 g feed stream 2 2.8 g feed stream 1: water 275 g Dowfax2A1 (45% strength) 38.9 g Disponil FES77 (30% strength) 5.8 g 7 g acrylic acid butanediol di Acrylate 0.7 g 3-mercaptopropyltrimethoxysilane 1.4 g styrene 318 g ethylhexyl acrylate 344.9 g ureidoethylene methacrylate (25% concentration in methyl methacrylate) 28 g.

Feed 2: Water 26.6 g Sodium peroxosulfate 1.4 g II. Preparation of tile adhesive and technical testing of application Tile adhesive was prepared by mixing the following components (parts are parts by weight) ).

Water 67 parts Lumiten® EL (antifoaming agent, BASF) 1 part Walocel® MW 40000 PFV (cellulose ether, Wolffwalside) 5 parts Example V1, V2 and dispersion of D1 to D4 202 parts Omycarb (R) 130 (Chalk, Omya) 290 parts Omyacarb (R) 40 (Chalk, Omya) 435 parts.

Shear strength The shear strength test was carried out according to DIN EN 1324 (3/9).
9).

Shear strength 1: Shear strength after 14 days storage in standard climatic conditions and 7 days storage in water.

Shear strength 2: Shear strength after storage for 7 days under standard climatic conditions and storage for 14 days at 70 ° C., tests were carried out using warm samples.

Results:

[0126]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09J 131/02 C09J 131/02 133/06 133/06 133/18 133/18 201/02 201/02 201 DG201 Inventor Hans-Jürgen Denu Germany Friedelsheim Waltershoehe 18 (72) Inventor Rolf Gulden Germany Frankenthal Pilstrasse 4 F-term (reference) 4H017 AA04 AA39 AB01 AB03 AB15 AC05 AD06 4J002 AA071 BC071 BC101 BG041 BQ001 DE026 GH01 GJ01 GJ02 HA07 4J040 DF041 DF051 GA03 GA05 GA07 GA08 GA11 GA19 GA24 GA30 JA03 LA06 LA07 LA08 MA04 MA06

Claims (11)

[Claims] 1. In an aqueous polymer dispersion, 0.0001 to 1 mol of a hydrolyzable silicon group and 0.0001 to 1 mol of a urea group or a thiourea group are added to 100 g of the polymer present in the dispersion. An aqueous polymer dispersion containing 1 mol. 2. The aqueous polymer dispersion according to claim 1, which is an aqueous dispersion of a radically polymerized polymer. 3. The aqueous polymer dispersion according to claim 1, wherein a urea group or a thiourea group is bonded to the polymer. 4. A urea or thiourea group having the formula I: (Wherein R ¹ and R ² independently represent a hydrogen atom or a C ₁ -C ₅ -alkyl group, or R ¹ and R 2
² together represent a bridged C ₂ -C ₄ -alkylene group, which may be mono- or disubstituted by a C ₁ -C ₄ -alkoxy group or a hydroxyl group, and X represents O or S 4. The aqueous polymer dispersion according to claim 3, which is a group of 5. A urea or thiourea group having the formula II: (Wherein, R ¹ and R ² represent the same as described above, R ³ represents a hydrogen atom or a methyl group, and Y represents —O— or —NH
- it represents, ^{R 4} is _C 1 _{-C 10} - represents an alkylene group)
The aqueous polymer dispersion according to claim 3 or 4, wherein the aqueous polymer dispersion is bonded to the polymer by copolymerization with an ethylenically unsaturated compound. 6. The aqueous polymer dispersion according to claim 1, wherein a hydrolyzable silicon group is bonded to the polymer. 7. The hydrolyzable silicon group of the formula III: Wherein R ^{5 to} R ⁷ independently represent a C _{1 to} C ₈ -alkyl group or an alkoxy group, provided that at least one of the groups R ^{5 to} R ⁷ represents an alkoxy group. 7. The aqueous polymer dispersion according to any one of 1 to 6. 8. The method according to claim 1, wherein a urea group or a thiourea group and a hydrolyzable silicon group are bonded to the polymer.
The aqueous polymer dispersion according to any one of the above. 9. The dispersion of the polymer, in the range of at least up to 40% by weight, of C ₁ -C ₂₀ -alkyl (meth) acrylates, vinyl esters of carboxylic acids having up to 20 carbon atoms, up to 20 carbon atoms Atom-containing aromatic vinyl compounds, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols having 10 to 10 carbon atoms, 1 to 2 carbon atoms having 2 to 8 carbon atoms The aqueous polymer dispersion according to any one of claims 1 to 7, comprising a so-called main monomer selected from the group consisting of aliphatic hydrocarbons having the following or a mixture of these monomers. 10. Use of the aqueous polymer dispersion according to claim 1 as a sealing material or a binder for an adhesive. 11. A binder for a tile adhesive as claimed in claim 1.
10. A method using the aqueous polymer dispersion according to any one of items 1 to 9.